A structural and electrochemical investigation of 1-alkyl-3-methylimidazollum salts of the nitratodioxouranate(VI) anions [{UO2(NO3)(2)}(2)(mu(4)-C2O4)](2-), [UO2(NO3)(3)](-), and [UO2(NO3)(4)](2-)

The properties of the 1-butyl-3-methylimidazolium salt of the dinuclear mu(4)-(O,O,O',O'-ethane-1,2-dioato)bis[bis-(nitrato-O,O)dioxouranate(VI)] anion have been investigated using electrochemistry, single-crystal X-ray crystallography, and extended X-ray absorbance fine structure spectroscopy: the anion structures from these last two techniques are in excellent agreement with each other. Electrochemical reduction of the complex leads to the a two-electron metal-centered reduction of U(VI) to U(IV), and the production Of UO2, or a complex containing UO2. Under normal conditions, this leads to the coating of the electrode with a passivating film. The presence of volatile organic compounds in the ionic liquids 1-alkyl-3-methylimidazolium nitrate (where the 1-alkyl chain was methyl, ethyl, propyl, butyl, pentyl, hexyl, dodecyl, hexadecyl, or octadecyl) during the oxidative dissolution of uranium(IV) oxide led to the formation of a yellow precipitate. To understand the effect of the cation upon the composition and structure of the precipitates, 1-alkyl-3-methylimidazolium salts of a number of nitratodioxouranate(VI) complexes were synthesized and then analyzed using X-ray crystallography. It was demonstrated that the length of the 1-alkyl chain played an important role, not only in the composition of the complex salt, but also in the synthesis of dinuclear anions containing the bridging mu(4)-(O,O,O',O'-ethane-1,2-dioato), or oxalato, ligand, by protecting it from further oxidation.

Half-precessional dynamics of monsoon rainfall near the East African Equator

External climate forcings-such as long-term changes in solar insolation-generate different climate responses in tropical and high latitude regions(1). Documenting the spatial and temporal variability of past climates is therefore critical for understanding how such forcings are translated into regional climate variability. In contrast to the data-richmiddle and high latitudes, high-quality climate-proxy records from equatorial regions are relatively few(2-4), especially from regions experiencing the bimodal seasonal rainfall distribution associated with twice-annual passage of the Intertropical Convergence Zone. Here we present a continuous and well-resolved climate-proxy record of hydrological variability during the past 25,000 years from equatorial East Africa. Our results, based on complementary evidence from seismic-reflection stratigraphy and organic biomarker molecules in the sediment record of Lake Challa near Mount Kilimanjaro, reveal that monsoon rainfall in this region varied at half-precessional (similar to 11,500-year) intervals in phase with orbitally controlled insolation forcing. The southeasterly and northeasterly monsoons that advect moisture from the western Indian Ocean were strengthened in alternation when the inter-hemispheric insolation gradient was at a maximum; dry conditions prevailed when neither monsoon was intensified and modest local March or September insolation weakened the rain season that followed. On sub-millennial timescales, the temporal pattern of hydrological change on the East African Equator bears clear high-northern-latitude signatures, but on the orbital timescale it mainly responded to low-latitude insolation forcing. Predominance of low-latitude climate processes in this monsoon region can be attributed to the low-latitude position of its continental regions of surface air flow convergence, and its relative isolation from the Atlantic Ocean, where prominent meridional overturning circulation more tightly couples low-latitude climate regimes to high-latitude boundary conditions.

Synthesis, Structure, and Spectroscopic Properties of the New Lanthanum(III) Fluoride Oxomolybdate(VI) La3FMo4O16

La3FMo4O16 crystallizes in the triclinic crystal system with space group P (1) over bar [a = 724.86(2) pm, b = 742.26(2) pm, c = 1469.59(3) pm, a = 101.683(2)degrees, beta 102.118(2)degrees, gamma = 100.279(2)degrees] with two formula units per unit cell. The three crystallographically independent La3+ cations show a coordination number of nine each, with one F- and eight O2- anions forming distorted monocapped square antiprisms. The fluoride anion is coordinated by all three lanthanum cations to form a nearly planar triangle. Besides three crystallographically independent tetrahedral [MoO4](2-) units, a fourth one with a higher coordination number (CN = 4 +1) can be found in the crystal structure, forming a dimeric entity with a formula of [Mo2O8](4-) consisting of two edge-connected square pyramids. Several spectroscopic measurements were performed on the title compound, such as infrared, Raman, and diffuse reflectance spectroscopy. Furthermore, La3FMo4O16 was investigated for its capacity to work as host material for doping with luminescent active cations, such as Ce3+ or Pr3+. Therefore, luminescence spectroscopic as well as EPR measurements were performed with doped samples of the title compound. Both the pure and the doped compounds can be synthesized by fusing La2O3, LaF3 and MoO3 (ratio 4:1:12; ca. 1 % CeF3 and PrF3 as dopant, respectively) in evacuated silica ampoules at 850 degrees C for 7 d.

Satellite tracking of the World's largest bony fish, the ocean sunfish (Mola mola L.) in the North East Atlantic

Satellite-linked archival transmitters were used to record the movements of three ocean sunfish (Mola mola) in the North East Atlantic. Patterns of depth use and temperature experienced by individual fish were integrated into 4-hour intervals throughout the tracking period and relayed via the Argos system. Data were recorded for 42, 90 and 54 days respectively from the three fish. The first two were tagged off southern Portugal at the end of February 2007 and travelled principally northward, while the third fish was tagged off west Ireland in August 2007 and travelled southward. These patterns are consistent with seasonal migration of ocean sunfish to high latitudes and their Subsequent return south. Maximum depths recorded by the three fish were 432 m, 472 m and 320 m respectively. All three individuals showed a diel pattern in depth use, occurring deeper during the day and shallower at night, a pattern consistent with sunfish tracking normally vertically migrating prey. Sunfish sometimes remained continuously at deeper (>200 m) depths during the day, but at other times they showed extensive movement through the water column typically travelling between their maximum depth and the surface within each 4-h period. The overall pattern to emerge was that ocean sunfish travel extensively in both horizontal and vertical dimensions, presumably in search of their patchily-distributed jellyfish prey.

The Type VI secretion system of Burkholderia cenocepacia affects multiple Rho family GTPases disrupting the actin cytoskeleton and the assembly of NADPH oxidase complex in macrophages

Burkholderia cenocepacia is a Gram-negative opportunistic pathogen of patients with cystic fibrosis and chronic granulomatous disease. The bacterium survives intracellularly in macrophages within a membrane-bound vacuole (BcCV) that precludes the fusion with lysosomes. The underlying cellular mechanisms and bacterial molecules mediating these phenotypes are unknown. Here, we show that intracellular B. cenocepacia expressing a type VI secretion system (T6SS) affects the activation of the Rac1 and Cdc42 RhoGTPase by reducing the cellular pool of GTP-bound Rac1 and Cdc42. The T6SS also increases the cellular pool of GTP-bound RhoA and decreases cofilin activity. These effects lead to abnormal actin polymerization causing collapse of lamellipodia and failure to retract the uropod. The T6SS also prevents the recruitment of soluble subunits of the NADPH oxidase complex including Rac1 to the BcCV membrane, but is not involved in the BcCV maturation arrest. Therefore, T6SS-mediated deregulation of Rho family GTPases is a common mechanism linking disruption of the actin cytoskeleton and delayed NADPH oxidase activation in macrophages infected with B. cenocepacia.